The present invention relates to the hydrometallurgical processing of nickel laterite ores and, in particular, to an improved method and system for selectively removing manganese (Mn) from nickel laterite waste liquors, allowing the effluent stream to be safely discharged to the environment.
Most of the world's remaining nickel (Ni) resources are contained in nickel laterites. These oxidic ores attracted considerable attention from nickel producers in recent years, especially for the application of leaching technology. This was partly due to advancements in pressure autoclave technology and materials of construction, large available ore bodies, and amenability of deposits to surface mining methods. The low-Mg, high-Fe limonitic fraction of the laterite profile is best suited for hydrometallurgical processing. The laterite projects developed over the past 15 years used exclusively high-pressure acid leaching (HPAL) to process the limonitic ores.
An important consideration in the processing of the limonitic ores is the disposal of waste products. Typically, large waste streams are generated in the process. A plant that produces 60,000 tonnes/year nickel could generate 2000-3000 m3/h of liquid waste. These large volumes arise from the need to process large tonnage of ores since the grade of the limonitic ore (1-1.6% Ni) is relatively low and the ore is not amenable to standard concentration methods owing to the presence of the paymetals (nickel and cobalt) in solid solution within the host minerals.
The HPAL process dissolves most of the ore solids releasing both the paymetals and the associated impurities. The main impurities are iron (Fe), manganese (Mn), aluminum (Al), silicon (Si), chromium (Cr), and magnesium (Mg). Some of the impurities, notably Fe, enter the solution and then undergo hydrolytic precipitation reactions within the autoclave and report to the leach residue. Despite this initial rejection of impurities, the autoclave discharge still contains significant amounts of impurities, which are separated in a series of unit operations.
Manganese and magnesium are two elements that dissolve in the autoclave and persist in solution. The waste liquor from the HPAL process typically contains about 1-3 g/L Mn and 2-15 g/L Mg, depending on the feed composition. Manganese is an environmentally regulated element requiring removal to less than 1 mg/L before the treated liquid stream can be safely discharged to the environment.
The standard practice used in the recently proposed laterite projects is to remove the Mn in the effluent stream as Mn(OH)2 by pH adjustment using lime neutralization. A pH in the range 8.5-9.5 is required to achieve less than 1 mg/L Mn. The main drawbacks of this approach are high reagent consumption due to the co-precipitation of nearly all the Mg (>98% Mg precipitation) as Mg(OH)2 and poor settling properties of the precipitated mixed Mn/Mg hydroxide product. The hydroxide product is gelatinous and difficult to handle and pump. Also, the additional Mg precipitation increases the tailings tonnage, and since the mixed hydroxide product is low-density, the consolidated settled density of the tailings in the storage pond is lower, significantly raising the required annual storage volume.
An alternative approach is to use oxidative methods to precipitate Mn. The oxide product settles and filters well. However, it has a high oxidizing capacity and there exists the possibility of undesirable side reactions during the disposal and storage of the Mn oxide waste stream; it is known, for example, that the manganese oxide product can oxidize chromium that is universally present in the effluent residues, releasing toxic hexavalent chromium (Cr6+)) into the residue pond water. Also, the removal of all the Mn by oxidative methods alone will be uneconomical because of the high level of Mn in the effluent stream and the high cost of oxidants.
Manganese can be readily oxidized to Mn (IV) and precipitated using many oxidants, such a mixture of SO2 and O2 or air. However, the SO2/O2 chemistry is not well understood and each aqueous system will have a different response to the application of this oxidant, depending on the prevailing chemistry of the system.
Berglund et al. reported that the addition of Mn3+ significantly increased the oxidation rate of Mn2+. See [1] J. Berglund, S. Fronaeus, and L. I. Elding, “Kinetics and Mechanism for Manganese-Catalyzed Oxidation of Sulfur(IV) by Oxygen in Aqueous Solution” Inorg. Chem. 32 (1993): p. 4527-4538; [2] J. Berglund and L. I. Elding, “Reaction of Peroxomonosulfate Radical with Manganese(II) in Acidic Aqueous Solution” J. Chem. Soc., Faraday Trans, 90 (21), (1994): p. 3309-3313. Zhang et al. showed that the addition of 2.7 mM hydroquinone, which is a free radical scavenger and effective reductant of Mn3+ and peroxy species, could completely stop the oxidation reaction. See [3] W. Zhang, P. Singh, D. Muir, “Oxidative Precipitation of Manganese with SO2/O2 and Separation from Cobalt and Nickel”, Hydrometallurgy 63, 2002, pp. 127-135; [4] W. Zhang, “SO2/O2 as an Oxidant in Hydrometallurgy”, Ph.D. Thesis, Murdoch University, Western Australia, February 2000.
Several patents have been filed for the use of SO2/air in effluent treatment: for mine drainage and waste pickling liquor (U.S. Pat. No. 3,738,932), for removing heavy metals from wastewater (Canadian Pat. No. 1,183,974), for removing arsenic from solutions containing sulfur dioxide (Canadian Pat. No. 2,255,874), and for removing cyanide, arsenic, and antimony from effluent streams (Canadian Pat. No. 1,241,774). These effluent streams have entirely different properties and requirements from those of laterite leaching waste liquors.
Various methods for the removal of Mn using the SO2/O2 or air method are known. Examples of such methods are taught in WO 00/56943 and WO 03/054238. However, both references are concerned with the purification of cobalt (Co) solutions and neither refers to the treatment of laterite waste liquors or, more importantly, the need to reduce total Mn to extremely low levels, less than 1 mg/L.